Carbamate esters of 2-hydroxy-3,4,5-trichlorobenzenesulfonamides

ABSTRACT

Novel carbamate esters of 2-hydroxy-3,4,5trichlorobenzenesulfonamides are prepared by the reaction of a 2hydroxy-3,4,5-trichlorobenzenesulfonamide compound with a substituted isocyanate compound in the presence of an inert carrier as a reaction medium at a temperature of from about 0* to about 100* C. for a period of about 1 to about 5 hours. The novel compounds are suitable for use as herbicides and fungicides.

United States Patent [191 Rodia et al.

CARBAMATE ESTERS OF 2-HYDROXY-3,4,5-TRICHLOROBEN- ZENESULFONAMIDES Inventors: Ralph M. Rodia; R. Garth Pews,

both of Midland, Mich.

The Dow Chemical Company, Midland, Mich.

Filed: Oct. 2, 1970 Appl. No.: 77,703

Assignee:

US. Cl. 260/468 E, 71/103, 260/472,

260/479 C, 260/556 AR, 424/300 Int. Cl. C076 125/06 Field of Search 260/468 E, 472, 479 C References Cited UNITED STATES PATENTS 2/1969 Gier et a1, 260/471 C 1 1 Apr. 9, 1974 3,577,453 5/1971 Rohr et a1. 260/471 C 3,609,177 9/1971 Traber et a1.. 260/471 C 3,649,671 3/1972 Kelyman 260/479 C Primary Examiner-Lorraine A. Weinberger Assistant ExaminerL. Arnold Thaxton Attorney, Agent, or Firm-Gary D. Street [5 7] ABSTRACT 8 Claims, No Drawings CARBAMATE ESTERS or Y RQ flEIQHPQBQQEEZEWHP- FONAMIDES SUMMARY OF THE INVENTION The present invention is directed to novel carbamate esters of 2-hydroxy-3,4,5-trichlorobenzenesulfonamides, to novel intermediates, and to methods for their preparation. The novel compounds of the present invention are represented by the following structural formula:

i o-ii-N-R R1 som wherein, in the above and succeeding formulas,

R is a member of the group consisting of loweralkyl, cycloalkyl, alkylene, naphthalene, phenyl and halophenyl;

R and R are members of the group consisting of hydrogen, cyclohexane, and loweralkyl of from one to about four, both inclusive, carbon atoms, with the proviso that when either of R or R is cyclohexane, the other of R or R is hydrogen or lower alkyl.

As used herein, the term loweralkyl means saturated, monovalent aliphatic-radicals, including straight and branched-chain radicals of from one to about six carbon atoms, as illustrated by, but not limited to, methyl, ethyl, propyl, isopropyl, butyl, sec.-butyl, amyl, hexyl, and the like.

As, used herein, the term cycloalkyl means cyclic, saturated aliphatic-radicals of from three to. eight carbon atoms, as illustrated by, but not limited to, cyclopropyl, cyclobutyl, 2-methylcyclobutyl, cyclohexyl, 4-. methylcyclohexyl, cyclooctyl, and the like.

The term alkylene as employed in the present specification and claims refers to straight-chain divalent radicals as well as to. branched-chain. divalent radicals of from two toabout six carbon atoms, as illustrated by, but not limited to,.ethylene, propene, butene, Z-butene, pentene Z-pentene, trimethylethylene, hexene, 2 -hexene, tetramethylethylene, and the like.

The term hal0phenyl" as used in the present specification refers to phenyl groups substituted with from one to three substituents. Suitable substituents, include bromine, chlorine, and fluorine.

The compounds of the, present invention are crystal"- linesolids and are of low solubility in water and of varying degrees of solubility in many common organic solvents. The novel' compounds are suitable for use as herbicid'es and fungicides and are especially adapted to be employed as active toxicantsv in herbicidal and fungicidal compositions.

The compounds of the present invention corresponding to Formula I areprepared by a novel process wherein a, 2-hydroxy-3,4',5-trichlorobenzenesulfonamide reactant of Formula II (hereinafter referred to as the benzenesulfonamide reactant), is reacted withv a substituted isocyanate compoundaccording to the following reaction sequence:

l /R SOQN wherein R, R and R are as previously defined.

The reaction of the benzenesulfonamide and isocyanate reactants is conveniently carried out in the presence of an inert carrier as a reaction medium. Representative inert carriers which can be employed as reaction media include carbon tetrachloride, chloroform, benzene, methylenechloride, acetonitrile,- and the like. In order to decrease reaction time, a small amount of an actuating agent, e.g., triethylamine, pyridine and the like, can be incorporated into the reaction mixture. In the present invention, the use of such actuating agents is preferred. The reaction proceeds readily at temperatures between 0 and 100 C.; generally, the reaction mixture can be heated at the boiling temperature under reflux. The pressure is not critical and is usually maintained at ambient atmospheric pressure.

In carrying out thereaction, the reactants are contacted with one another in a reaction medium as described. Typically, the benzenesulfonamide reactant and actuating agent are dispersed in a liquid reaction Cl C 1 medium and the isocyanate reactant is added dropwise thereto. The resulting reaction mass is generally maintained at the boiling temperature under reflux for a sufficient period of time to allow substantial completion of the reaction, usually from about 1 to about 5 hours. Following the substantial completion of the reaction, the reaction mass is cooled, diluted with a suitable organic solvent, such as one of those hereinbefore mentioned, and evaporated to dryness under reduced pressure. The residue representing the desired product can be further purified by utilizing conventional techniques which include washing with a liquid which is a solvent for imputies but not for the product, recrystallization,

and the like.

In a further embodiment of the present invention, the 7 compounds of Formula II are prepared bydissolving a 2,3,4,5-tetrachlorobenzenesulfonamide compound in a liquid reaction medium, such as, for example, any of those mentioned hereinbefore. The mixture is heated and maintained at its boiling temperature under reflux DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples illustrate the invention but .ars q t9 2. .qe s r asl aitipsthc same- 3 EXAMPLE 1 N ,N-diethyl-Z-hyd roxy-3 ,4'-,5 -trichlorobenzenesulfonamide (5.0 grams, 0.015 mole) was dissolved in 25 milliliters of chloroform containing 2 to 3 drops of triethylaminc and the resulting mixture was heated at the boiling temperature under reflux. Ally] isocyanate (3.0 grams; 0.036 mole) was added dropwise to the refluxing mixture over a period of from about 3 to about 10 minutes and the resulting reaction mixture was maintained at the boiling temperature under reflux for a period of about one and one-half hours. Following the completion of the reaction, the reaction mixture was cooled and diluted with methylenechloride. Removal of the solvent present in the reaction mixture was accomplished by evaporation under reduced pressure, and the residue thus obtained was recrystallized from a hexaneme h n Ch or de 91l4 i9' -A a e ltqf L H??? ears;

tions, the desired 2,3,4-trichlor -6-(diethylsulfamoyl)phenyl allylcarbamate product was obtained as a crystalline solid melting at l21l 27 C. Elemental analysis calculated for C H N Cl O S (percent): C, 40.5; H, 4.1; N, 6.9; Cl, 25.6; S, 7.7. cent): C, 40.7; H, 4.1; N, 6.7; CI, 26.0; S, 7.8.

Other representative products of the present invention are prepared according to the procedure of Example 1 above, using the respective corresponding benzenesulfonamide and ,isocyanate reactants. These other representative products are identified in the following table I-wherein R,'R and R have the same significance as set forth hereinbefore;

MP is melting point; and M.VYJ!99 999LM w i ht 7.

Found (peri i 0-c-N-R R1 C1 OIN Identlt of com 11nd y p0 Characterizing Ex. No. R R1 R: property 2 C --c|m -c,m MP loo-110 c.

a J1 c,H, --c,H, MP 161170 o.

4 c1 -c,m 43,11, MP 164-112 0.

s c,m -c,H5 MP nae-149 c.

6 -CH4 C1H -C:Hs MW 389- 5 1 -c,H5 -c,m MP 149-151" 0.

s -C\Hl H -c.H. MW 431. 5 9 -CIH13 -C3H1 --C:H1 MW 487.5

10. -C Hu -rr MW 471.5

11 -c,H1 -c,m MW 411.5

12 -c.a. H -H MW 315.5

13 H MW 483.5 H H 14 6) 41,111 -c,1 11 Mwsias 15 C{Hn -H MW 429-5 16 Same as above --c,m MW 483.5

terms-.. crat Identity of compound Ch EX. N0. R R1 R3 fi fig E111.I.I.i f fifijf fifiiifi fii w I -3 W "v C511 w MW M35 19 -CH:(CH7):CH=CH2 -H MW 469.5

20 -CH,CH=0HOH, -H -H MW 373.5 21 CH7(CH:):CH=CH1 CH3 -C3H1 MW 4435 22 H C3H1 MW 437.5

23 Same as above. H' H MW 527.5

24 d0 -H -H MW'445.5

25 1E1. CaH'1 CaH1 MW 637.5

26 (I31 C3Hs C:H5 MW 555 27 1'31 H H MW 632.5

28 Br H MW 635.5

29 01 -C:Hl MW 574.5

EXAMPLE 30 40 mid e, having a molecular weight $331.5; N,N-diethyl-2,3,4,5'-tetrachlorobenzenesulfonamide 'll py j y y 'l (5.0 grams) was dissolved in 30 milliliters of methanol fonamlde, havmg a molecular welght of 360-5; and heated at the boiling temperature, under reflux. To N-cyclohexyl-2-hydroxy3,4,S-trIChIQPObePRHeSUL this refluxing mixture was added; by dropwise addition fonamlde havmg a molecular weight 9 over a period of about 3 to 10 minutes, a solutionof poy y ydr0Xy-3,4,5-tr1chlorobentassium hydroxide (15.0 grams) in 30 milliliters of wa- Zenesulfonamlde, havmg almoleculal' weight of ter; The resulting reaction mixture was maintained, at the boiling temperature under reflux for a period of r f y i' y' Q E L from about 8 to-about 14 hours. Following the complefonamlde, havlng a molecfllar Weight of tion' of the reaction, the reaction mixture was cooled -Pr Py -l y y- A, hl r benzenesulfonaand acidified to a pH of 1.0 with concentratedv hydromlde, havmg a molecular welght chloric acid. The solid product formed upon acidifiy P 'Py y Y ncation was filtered off and recrystallizedfrom an etherzenesulfoflamiderhaving ula W ight 0f'33- hexane mixture. As a result of these, operations, there and 2-hydroxy-3,4,5-trichlorobenzenesulfonamide, havwas obtained the desired N,N-diethyl-2-hydroxy-3,4,5- trichlorobenzenesulfonamide compound melting at l44l4.7 C. Elemental analysis calculated for (percent): C H Cl SO N: C, 36.5; H, 3.69; N, 4.23; Cl, 31.6; S, 9.9. Found (percent): C, 36.5; H, 3.74; N 4.26; Cl, 31.5; S, 10.1.

In a manner similar to that described in Example 30, there are obtained, inter alia, the following 2-hydroxybenzenesulfonamide compounds upon the reaction of the respective corresponding 2,3,4,5-tetrachlorobenzenesulfonamide compound with potassium hydroxide:

' N-butyl-2-hydroxy-3,4,5-trichlorobenzenesulfonapounds, or a solid composition comprising the compound, can be dispersed in water, typically with the aid of a wetting agent, and the resulting aqueous suspension employed as a spray. in other procedures, the

such plant pests are contacted with one of the above named compounds at a dosage of 20 pounds per acre.

The 2,3,4,5-tetrachlorobenzenesult'onamide compounds and the substituted isocyanates of the type emcompound can be employed as a constituent oil organic ployed as starting materials in the present invention can liquid compositions, oil-in-water and water-in-oil emulbe prepared by known or analogous conventional sions, or water dispersions, with or without the addition methods or readily obtained from commercial sources. of wetting, dispersing, or emulsifying agents. W e claim: V H The exact concentration of the toxic constituent to 1. Compounds corresponding to the formula: be employed in the treating compositions is not critical to and may vary considerably provided the plant or fungal f oif pests and/or their habitats are contacted with an effecy;. i; tive amount of the toxicant. Good results are obtained when compositions containing controlling and fungic1- SOZN cidal oncentrations, usually from about 500 to 10,000 15 R2 parts per million. by weight of one or more of the com-, 61 pounds, are employed. The concentration of toxicants in liquid compositions generally is from about 1.0 to 1 about 50 percent by weight. Concentrations up to 95 wherein Y 7 weight percent are often employed. In dusts, the con- R pr n a me 0f the group consisting of centration of the toxicant can be from about 1.0 to 10 alkyl groups containing from one to six carbon weight percent; however, concentrations up to 95 atoms, inclusive, cycloalkyl groups containing from weight percent are often conveniently employed. in three to eight carbon atoms, inclusive, alkylene compositions to be employed as concentrates, the toxig p containing from two to six carbon atoms. cant can be present in a concentration of from 5 to 98 inclusive, n -P p y and p y t in i h Pei-Cent, which halophenyl refers to phenyl groups substi- In representative operations numg ous compositions tuted from one to three substituents selected containing 500 parts of one of the-compounds of the from the group consisting of bromine, chlorine and present invention as sole toxicant per million parts by fluorine; weight of ultimate treating composition were prepared R1 and R2 r pre ent a member of the group consisting and separately applied to the enviroments containing of hy rogen, cyclohexane and alkyl groups conand supporting thriving members of one of a variety of mining one to four Carbon atoms inclusive, with fungal organisms. The results of the evaluations of the the proviso that when either of R or R is cyclocompounds tested at the above concentration and the hexane, the Other of Ref R is hydrogen or alkyl of present control of the organisms treated are set forth in from one to four carbon atoms, inclusive. the following table ll: 2. A compound according to claim 1 which is 2,3,4-

' TABLE II Percent control and kill of- Com and um r Identity of compound Bar. S41. "Tan. M42.

1 2,3,4-triehloro-6-(diethylsu1tamoyl)phenyl methylcarbamate 100 0 100 2 2,3,4-trlchloro-G-(diethylsultamoyl)phenyl allylcarbamate 100 100 0 50 3. j. 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl m-ch10rocarbanilate- 100 100 100 100 4. 2,3,4-triehloro-fi-(diethylsultamoyl)phenyl a-naphthalenecarbamate 100 50 0 100 5.. 2,3,4-triehloro-6-(diethylsultamoyl)-phenyl carbanilate 100 100 100 100 6 2,3,4-trlchloro-6-(diethy1suliamoyl)phenyl 3,4-dich1orosarbanilate-- 100 100 100 100 7 2,3,4-triehlor0-6-(diethy1sulfamoyl)phenyl cyclohexylcarbamste 100 50 0 100 'B.S.=Becillua aubtilia; S.a.=Staphz loc0cczts aureua: T.m.=flrichoph lton mcntagrophytea; M.p.=Mucobucterium phlei.

lri tii'rtlier representativeoperations, each of the 2? 4-trichloro-6-(diethylsulfamoyl)phenyl methylcarbamate, 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl allylcarbam ate, 2 ,3 ,4-trichloro-6-(diethylsulfamoyl )phenyl m-chlorocarbanilate, 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl a-naphthalenecarbamate, and 2,3,4- trichloro-6-(diethylsulfamoyl)phenyl cyclohexanecarbamate compounds gives complete control and kill of cotton when one of the named compounds is separately applied to cotton plants at a concentration of 4.0 parts 'trichloro-6-( diethylsulfamoyl )phenyl 

2. A compound according to claim 1 which is 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl methylcarbamate.
 3. A compOund according to claim 1 which is 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl allylcarbamate.
 4. A compound according to claim 1 which is 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl m-chlorocarbanilate.
 5. A compound according to claim 1 which is 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl carbanilate.
 6. A compound according to claim 1 which is 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl Alpha -naphthalenecarbamate.
 7. A compound according to claim 1 which is 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl 3,4-dichlorocarbanilate.
 8. A compound according to claim 1 which is 2,3,4-trichloro-6-(diethylsulfamoyl)phenyl cyclohexanecarbamate. 